JPH02143247A - Image forming method - Google Patents

Abstract

PURPOSE:To shorten the time for developing by processing the silver halide color photographic sensitive material contg. diffusion resistant couplers and diffusion resistant color developing agents on a base by a color developing soln. contg. the diffusive arom. primary amine color developing agents. CONSTITUTION:The silver halide color photographic sensitive material contg. the diffusion resistant couplers and the diffusion resistant color developing agents on the base is processed by the color developing soln. contg. the diffusive arom. primary amine color developing agents. The diffusion resistant color developing agents are simultaneously incorporated into the photosensitive material in the image forming method which uses the color developing soln. contg. the diffusive color developing agents in such a manner. The coupling reaction is greatly accelerated in this way and the time for processing is shortened.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a photographic material having a layer containing a diffusion-resistant coupler and a diffusion-resistant color developing agent. The present invention relates to a method for developing with a color developing solution containing the following, and relates to an image forming method for rapidly and stably forming a dye image.

(Prior Art) A general method for forming images using silver halide color photographic light-sensitive materials is to use silver halide in the presence of a color coupler that has the ability to react with an oxidized form of a developing agent to form a dye. This is a method of obtaining an azomethine or indoaniline dye by developing a photosensitive material using a color developing solution containing an aromatic primary amine color developing agent.

This color development method was basically developed in 1935, D, M
Annes & L. Godowsky, and it is used worldwide today with various improvements.

The processing process for color photographic materials basically consists of the following three steps.

(1) Color development process (2) Bleaching process (3) Fixing process The bleaching and fixing steps can also be carried out simultaneously.

That is, it is a bleach-fixing process (so-called Brix), in which developed silver and undeveloped silver halide are desilvered. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process also includes auxiliary steps to maintain the photographic properties and physical quality of the image, or to improve the storage stability of the image. It is also accompanied by For example, a curing bath to prevent excessive softening of the photosensitive film during processing, a stop bath to effectively stop the development reaction, an image stabilizing bath to stabilize the image, and a film removal bath to remove the backing layer of the support. Processes such as bathing are mentioned.

In the color development process, an aromatic primary amine color developing agent dissolved in an alkaline aqueous solution is used as a color developer. This aromatic primary amine color developing agent permeates into the photosensitive film and develops (reduces) the exposed silver halide, while the developing agent itself is oxidized by the silver halide and becomes an oxidized product. Further, this developing main straw oxidized product diffuses in the gelatin film and couples with the coupler dispersed in advance by the oil protection method to form a dye.

In recent years, processing solutions in which benzyl alcohol has been removed from color development processing solutions have become mainstream in order to reduce the pollution load. When processed with a color developing solution that does not contain benzyl alcohol, it is sensitized and the maximum color density (Dg + a
x) shows the behavior of decreasing.

Furthermore, in response to the demand for photosensitive materials with high image quality and high sharpness, attempts have been made to reduce the blurring effect caused by light scattering by making the emulsion film thinner. One such technique is to reduce the ratio of the oil in which the coupler is dispersed to the coupler. When the oil/coupler ratio is reduced, the same decrease in PJDtaax occurs as in the case of processing with a processing solution that excludes benzyl alcohol.

As a means of solving the problem of reduced development activity and resulting loss of speed, the p
A known method is to increase H and processing temperature to accelerate development. However, this method has serious problems such as high fog, poor stability of the developer, and increased fluctuations in photographic properties during continuous processing. As another accelerating technique, there is a method of adding various development accelerators, but the accelerating effect is insufficient and unsatisfactory.

In our research, we have found that color developing agents are distributed in the oil that disperses the couplers in the gelatin film during the color development process, and that the amount of distribution varies depending on the type of coupler or the dielectric constant of the oil. I found it. They also discovered the fact that the larger the amount of color developing agent distributed in the oil, the faster the color development speed of the sensitive material. In other words, the higher the concentration of the color developing agent in the oil, the faster the color development speed of the photosensitive material. We conducted further research and found that the speed of color development can be more effectively sensitized by incorporating a diffusion-resistant color developing agent into the oil in advance.

Based on the above knowledge, by incorporating a diffusion-resistant color developing agent together with a coupler, it has become possible to design a photosensitive material that has a fast color development rate and is less dependent on processing when developed with a developer. .

Several methods are known for incorporating a color developing agent into a light-sensitive material and developing it with an alkaline aqueous solution.

For example, U.S. Pat. No. 3,342,599 uses Schiff base with salicylaldehyde as a developing agent precursor. In US Pat. No. 3,719,492, metal salts such as lead and cadmium are used in combination. In British Patent No. 1,069,061, an aromatic primary amine and phthalic acid are reacted to form a phthalimide precursor. In Japanese Patent Application No. 52-26756, an aromatic primary amine and a cyclic β-dicarbonyl compound are used together. In Japanese Patent Application No. 52-50909, substituted or unsubstituted (2-benzenesulfonyl) with an aromatic primary amine
A precursor to which ethoxycarbonyl is bonded is used. Other German Patent No. 1,159.758, German Patent No. 1,200,6
No. 79, U.S. Patent No. 3,105,035, special +b”l
Known examples include Japanese Patent Publication No. 14838/1983, No. 14839/1983, Japanese Patent Publication No. 16730/1983, and No. 18732/1983.

The alkaline aqueous solution used to develop silver halide color photographic materials containing color developing agents or color developing agent precursors decomposes the color developing agent precursors and converts them into color developing agents. , in order to promote the reduction of developable silver halide to metallic silver by the color developing agent at a sufficiently high rate with respect to the dissolution rate of the color developing agent or the precursor of the color developing agent into the alkaline aqueous solution, compared to the conventional developer. A relatively high pH is also employed. The maximum pH depends on the combination of color coupler and color developing drug or color developing agent precursor, but usually ranges from about pH 10 to 14, preferably at p
It is used in the range of H11 to H13.

However, when such a high PM alkaline aqueous solution is used as a processing solution, it may be affected by, for example, the effects of carbon gas in the air or the effects of hydrogen ions generated in the photosensitive material during color development. The pH decreases, and it is very difficult to keep the pH of this alkaline aqueous solution stable. As the pH of the alkaline processing solution decreases, the development speed of the photosensitive material decreases significantly, and problems such as inconsistent finished quality and decreased maximum color density occur, especially in continuous processing.

Further, when a color developing agent precursor is incorporated into the sensitive material, it is necessary to first activate the color developing agent precursor with an alkaline aqueous solution. This activation process lengthens the color development processing time, which is undesirable from the viewpoint of speeding up the processing.

Due to the above-mentioned problems, photosensitive materials containing color developing agents or their precursors have not yet been put to practical use.

The present invention is characterized in that a light-sensitive material containing a diffusion-resistant coupler and a diffusion-resistant color developing agent is developed with a commonly used color developing solution containing an aromatic primary amine color developing agent. Therefore, the pH of the processing solution is within the commonly used pH range (pH 9 to 12).
In addition, in the present invention, a diffusion-resistant color developing agent is directly incorporated into the photosensitive material, so color development, which was a problem when using its precursor, is not a problem. It is advantageous for speeding up processing because it does not require an activation process from the main drug precursor.

Further, in U.S. Pat. By processing,
However, in this invention, the color developing agent contained in the photosensitive material is used to replenish the color developing agent in the color developing solution by flowing out into the processing solution. is required to be a color developing agent with diffusive development activity.

On the other hand, it is preferable that the color developing agent contained in the light-sensitive material used in the present invention does not flow out into the processing solution.

This is because, if a diffusible color developing agent that leaks into the processing solution is used, problems such as a decrease in the maximum color density, an increase in fluctuations in photographic properties during continuous processing, and a worsening of the stability of the processing solution. occurs. Therefore, the present invention is achieved by containing a diffusion-resistant color developing agent in an oil containing a diffusion-resistant coupler so that it will not flow out into the processing solution during the development process.

Also, JP-A-62-178962, JP-A No. 62-17896
No. 3 describes that a photosensitive material with excellent light fastness is provided by incorporating a p-phenylenediamine compound together with a cyan coupler, but the p-phenylenediamine compound used in these inventions Since it is used as a photofading inhibitor for cyan couplers, it is not necessary to have an unsubstituted amino group, that is, it is necessary to have coupling activity when oxidized.

On the other hand, in order to promote the diffusion-resistant it-developing agent used in the present invention, it is incorporated in the oil together with the diffusion-resistant coupler, and the color developing agent contained therein has an oxidized form that has a coupling activity with the coupler. Therefore, the above two inventions are completely different from the present invention.

An object of the present invention is to shorten the processing time by using a commonly used color developing solution containing an aromatic primary amine color developing agent, and to provide a stable image forming method with less processing dependence. It is something to do.

(Means for Solving the Problems) An object of the present invention is to produce a silver halide color photographic light-sensitive material containing a diffusive aromatic primary amine color developing agent on a support. This was achieved by an image forming method characterized by processing with a color developer containing a developing agent.

In this way, in an image forming method using a color developing solution containing a diffusive color developing agent, it was unexpected that the coupling reaction was significantly accelerated by incorporating a diffusive color developing agent into the photosensitive material at the same time. It was about.

Furthermore, the invention described in the above-mentioned US Pat. No. 4,297,437 is intended to cause the herbal medicine to flow out into the processing liquid, but the present invention is fundamentally different in that it prevents it from diffusing. Different.

The diffusion-resistant color developing agent used in the present invention includes:
An aromatic primary amine color developing agent represented by the following general formula (1) and having diffusion resistance is preferably used.

General Formula (1) In General Formula (1), R+ and Rz represent a hydrogen atom or an alkyl group, a cycloalkyl group, or an alkenyl group, and the alkyl group or alkenyl group may be linear or branched. (However, R8 and R7 may form a heterocycle with a nitrogen atom), and these alkyl groups, alkenyl groups, and cycloalkyl groups may form substituents [e.g., aryl groups, cyano groups, halogen atoms, heterocycles, alkyl groups, alkenyl groups, cyclo In addition to alkyl groups, acyl groups, carboxy groups,
Those substituted via a carbonyl group such as carbamoyl group, alkoxycarbonyl group, and aryloxycarbonyl group, and those substituted via a petero atom (specifically, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group) groups, acyloxy groups, carbamoyloxy groups that are substituted via an oxygen atom, nitro groups, amino groups (including dialkylamino groups, etc.), sulfamoylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, Those substituted via a nitrogen atom such as an acylamino group, sulfonamide group, imide group, or ureido group, or substituted via a sulfur atom such as an alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, or sulfamoyl group. or substituted via a phosphorus atom such as a phosphonyl group)].

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1.1' dibentynonyl group, 2
-Chloro-L-butyl group, trifluoromethyl group, ■-
Ethoxytridecyl group, l-methoxyisopropyl group,
methanesulfonylethyl group, 2.4-di-amylphenoxymethyl group, anilino group, l-phenylisopropyl group, 3-n-butanesulfonaminophenoxypropyl group, 3-4'-(α-(4' (p-hydroxybenzenesulfonyl)phenoxy] dodecanoylamino)phenylpropyl group, 3- (4'-[α-(2
',4'-di-t-amylphenoxy)butanamide]
phenyl)-propyl group, 4-[α-(0-chlorophenoxy]tetradecanamidophenoxy]propyl group,
Examples include allyl group, propenyl group, decenyl group, cyclopentyl group, and cyclohexyl group.

R1 and R4, Rs, and Rh are substituents that can be substituted on the benzene ring and are not particularly restricted, but specifically, hydrogen atoms,
Halogen atom, alkyl group, alkenyl group, aryl group, alkoxy group, alkenoxy group, aryloxy group,
Examples include an alkylthio group, an arylthio group, an acyl group, an acyloxy group, an acylamino group, an amino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. (However, R3 and/or R4 may form a 5-membered or 6-membered ring together with R1 and/or R2.) The diffusion-resistant color developing agent of general formula (1) according to the present invention may be a mineral acid (e.g. They are contained in sensitive materials as acid salts that can form salts with amines such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, etc.) and organic acids (such as methanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, etc.). It's okay.

The compound used in the present invention may be a variety of precursors of a color developing agent that releases the diffusion-resistant agent of the general formula (1) shown in the present invention in a color processing solution, but in the system of the present invention, In order to obtain a greater development accelerating effect, it is better to use a non-precursor agent, that is, a diffusion-resistant main agent that has development activity by itself.

The compound represented by the general formula (1) of the present invention is contained in a high boiling point organic solvent (oil) used for dispersing a diffusion-resistant coupler in a light-sensitive material for the purpose of accelerating the rate of dye formation in a color development process. added to. Therefore, it is preferable that the present compound does not flow out into the color processing solution.

For that purpose, in general formula (1), R7 and Rt,
The total number of carbon atoms in the substituents represented by , R1, Rs2, Rs2, and R1 is preferably 10 or more and 30 or less, most preferably 13 or more and 30 or less. Compounds that satisfy this condition have extremely low leakage from the light-sensitive material into the processing solution during color development processing, and their oil solubility increases, making them less susceptible to the effects of aqueous processing solutions.For example, they have significant resistance to hydrolysis. more effective.

Specific examples of the diffusion-resistant color developing agent used in the present invention are listed below, but the present invention is not limited thereto.

Ni.

The developing agent to be contained in the photosensitive material of the present invention can be prepared by known synthetic methods or synthetic methods similar thereto.For example, U.S. Pat. A synthesis example of the exemplified compound (5) of the present invention is given. In addition, there are examples of typical color developing agents such as U.S. Pat. The compounds of the present invention can be synthesized in a similar manner to that described above.

The usage amount of the diffusion-resistant color developing agent represented by the general formula [1] used in the present invention is 5% in a certain layer containing the splash-resistant diffusion coupler with respect to the diffusion-resistant coupler coated in the same layer. -200 mol% is preferable, and 5-100 mol% is more preferable.

These compounds are represented by the general formula (+).

It is usually dispersed in a hydrophilic colloid liquid with a diffusion-resistant coupler by an oil/water emulsion type dispersion process.

When oil is used in this way, the effects of the present invention are even more pronounced, and especially when used in the same oil phase as the diffusion-resistant coupler, remarkable effects can be obtained. However, it can also be used by directly dispersing it in a hydrophilic binder without using oil. The oil used in the oil/water emulsion type dispersion method, that is, the high boiling point organic solvent, is an oil for dissolving the coupler using an oil protection type as a material.
), (C), (D) and (E) are preferably used, and among these, those of the following general formulas (A) and (C) are particularly preferable from the viewpoint of accelerating development.
, (D) and (E).

General formula (A) W+ fortune telling General formula (B) w, -coo-w.

General formula (C) General formula (E) W, -0-W.

(In the formula, w, , Wl and W each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, and W4 is W,
represents OW or S-W, n is an integer from 0 to 5, and when n is 2 or more, W4 may be the same or different from each other; -In the general formula (E), WI and W8 may form a fused ring) The general formula (A), (B), (C), (D) or (E
) in the high boiling point organic solvent represented by substituents W, ,
The sum of carbon atoms in W, , W, or W is expressed by the general formula (A
), (B), (C), (D) or (E) of about 8 or more, and which corresponds to a dielectric constant of 4°00 or more (25°C).

In addition, electric current is determined by the converter bridge method (Ando Electric TR5-I).
It can be easily determined by measuring with OT).

In the general formula (A), (B), (C) or (E), when W, , W, and W have a (^ group), one or more substituents -C-- It may be a group having a bonding group selected from COO-/, -R@N (R1 is ゝN-, a divalent to hexavalent group obtained by removing a hydrogen atom from a phenyl group), and -〇-. .

In the general formula (A), (B), (C), (D) or (E), the alkyl group represented by WI, Wt, Ws or W may be linear or branched. For example, a methyl group , ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradisyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group group, nonadecyl group, eicosyl group, etc.

The permissible substituents for these alkyl groups are -71m
To explain the case of formula (A), for example, a halogen atom, a cycloalkyl group, an aryl group, an ester group, and examples of such substituted alkyl groups include substituted products of halogen (F, Cj!, Br) ( -CJIP+iC5
HsFs, CvllzF+i, C! H4CR,,Cs
1liCR1-csusscp”, C311SCI B
r.

C5HsBr! etc.), cycloalkyl group substituent Cl1
zC)IzCOOC+Jzs, (CIlt)ncOO
cHz (CPz) 4H1-(CIl mountain cooc mountain, -(
CH mountain, COOC mountain, etc.), substituent group that gives emulsion ester, etc. Substituent group that gives malic acid ester, etc. (CntCH<OK) C00CJ+2, etc.), substituent group that gives tartaric acid ester, etc. (-CH(OH)CH(Of
f) COOCJ + q A substituent that provides citric acid ester, etc.

Also in general formulas (B) to (sniff), the same substituents in the alkyl group of the general formula (A) may be substituted with the alkyl group.

Furthermore, in the general formula (E), R and R4 may be an oxirane ring, an oxirane ring, or an oxane ring forming a condensed ring.

Schiff C! denoted by W, ,W, ,W, or W!
Hs, substituted cyclohexyl group is for example CI.

These are the basics.

The aryl group represented by W', Wt, Wx or W4 is terephthalic acid, trimellitic acid ester, etc., and the aryl group is, for example, substituted benzoic acid ester such as CxI(s).

The alkenyl group is 10 4111, -CSH*, C41
111, CJ+i, CsH+s, CIIHI9
, C+tHzgo, CII)Iss, etc., and the substituted alkenyl group is, for example, a halogen atom (F, CLBr
), -0CIIIlff, a substituted group, C1l''
'Cfl C00CHzCHCaH9, preferably W
, , W, , W, or W4 substituents preferably have a dielectric constant of 5.0 or more at 25°C and a viscosity of cP or more at 25°C. It is surprising that this value of dielectric constant and viscosity improves the coloring properties without impairing the absorption or other effects of the coloring dye, and although the reason is not clear, it is probably due to the high boiling point organic matter with a high dielectric constant. The solvent has a high boiling point with a medium viscosity and a high uptake of the color developing agent. It is thought that the solvent weakens any adverse effects of the coupler in the oil droplet with the silver halide.

In the present invention, general formulas (A), (B), (C), (D
), and the amount of the high boiling point solvent represented by (E) is:
Any amount may be used depending on the type of coupler and the amount used, but the high boiling point organic solvent/coupler ratio by weight is 0.
It is preferable that it is 605-20. In addition, the general formula (A
), (B), (C), (D) and (E) according to the present invention may be used alone or in combination, or may be used in combination with other conventionally known It can also be used in combination with a high boiling point organic solvent. Examples of these conventionally known high boiling point organic solvents include tricresyl phosphate, tri-2-ethylhexyl phosphate,
Phosphate ester solvents such as 7-methyloctyl phosphate and tricyclohexyl phosphate, 2,5-di-tert-amylphenol, 2,5-di-tert-amylphenol, 2,5-di! 1ec
- Phenolic solvents such as amylphenol can be mentioned.

Specific examples of high boiling point organic solvents represented by general formulas (A), (B), (D) and (E) are shown below, but the invention is not limited thereto.

(S-1) 0=P-(-QC, H, -E).

(S-2) (S-3) 0 = P (OCa HI!n) 5 (S-4) (S-9) C1].

(S-10) 0 = Pro C, H, q-4so) 5(S-1
1) (S-12) o=p-+oc,. T”IfI n)3(S-6) 0=P (QC, H, -E).

(S-14) H3 C11゜(S-1,5) (S-20) (S-21,) (S-31) Js Cz If 5 (S (S-47) (S-48) (S- 49) CHCOOCIlz(ChCFz)J CIICOOCR□(CFzCFt)J(S (S-44) CH! COOC4Hq CH30CO-C-COOC4H? CHgCOOCnllv (S tns 80 CCOOCIIzCI ICJeC00CIIz
CIICJeCI1 tHs (S-54) (S-56) A diffusion-resistant coupler and a diffusion-resistant color developing agent represented by general formula (1) are mixed with oil/diffusivity in the above-mentioned high boiling point organic solvent.
For dispersion in the aqueous phase by the water emulsion type dispersion method, common surfactants are used. For example, anionic surfactants containing acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfur ester, phosphoric ester groups, etc., and nonionic surfactants. , cationic, and amphoteric surfactants are used.

As the hydrophilic colloid, those known as photographic binders including gelatin are used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfate, sodium alginate, starch derivatives, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of acids, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. Alternatively, latex etc. may be added. For example, US Patent No. 3,
Examples include the compounds described in No. 518,088.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing a diffusible aromatic primary amine color developing agent as a main component. More specifically, the diffusible color developing agent shown in the above general 2N) is used. The total number of carbon atoms in the substituents represented by RI, R, R, R, R, R, is preferably 9 or less (including 0), more preferably 3 to 8, particularly preferably 3 to 7, Although aminophenol compounds are also useful as color developing agents, p-phenylenediamine compounds are preferably used, and a typical example is 3-methyl-
4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-methanesulfonamidoethylaniline, 3-methyl-
Examples include 4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can also be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonate, triethylenediamine (1,4-diazabicyclo[2°2.2]octane), etc. Various preservatives such as ethylene glycol, diethylene glycol, etc. Solvents, development accelerators such as polyethylene glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developing agents such as l-phenyl-3-virazolidone, viscosity. various oxidizing agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid,
Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediamine tetra[, hydroxyethylimidiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
Typical examples include nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N, N%N',N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid) and their salts. can be raised. Note that it is preferable that benzyl alcohol is substantially not contained.

That is, it is preferably 5id/l or less, and more preferably Od/l.In other words, the diffusion-resistant color is better when a compound such as benzyl alcohol is not contained in the coloring liquid than when it is contained in the coloring liquid. The effect of containing the developing agent in the photosensitive material becomes more pronounced.

These color developing solutions generally have a pH of 9 to 12. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally 32 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be reduced to 500JD or less. You can also do that. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the liquid with the air. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process), or separately (bleach-fixing process), or in order to speed up the process, it may be possible to perform a bleach-fixing process after the bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■), Kobal) (I
II), compounds of polyvalent metals such as chromium (IV) and copper (II), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (Ill) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3- Aminopolycarbona such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, etc. [or complex salts of citric acid, tartaric acid, malic acid, etc.];
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron (I[I) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (III) iff salt, are preferable from the viewpoint of rapid processing and environmental pollution prevention. III) Complex salts are particularly useful both in bleaching solutions and in bleach-fixing solutions.

The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (Ill) complex salts is usually 565 to 8, but in order to speed up the processing, the pH can be lowered.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,983,858, Research Disclosure No.
Compounds having a mercapto group or disulfide group as described in JP-A No. 50-140.129; thiazolidine derivatives described in JP-A No. 45-8,506, JP-A No. 52-20゜832; 53-32.735, thiourea derivatives described in U.S. Patent No. 3,706,561;
6.235; West German Patent No. 966.4
10, polyoxyethylene compounds described in Japanese Patent Publication No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others described in Japanese Patent Publication No. 49-42,434, Japanese Patent Publication No. 49-42,434.
No. 9-59,644, No. 53-94,927, No. 54
-35,727, 55-26.506, 5B-
Compounds described in No. 163゜940; bromide ions, etc. can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and in particular, U.S. Pat. No. 3,893,858 and West German Patent No. 1.29
No. 0,812, JP-A No. 53-95,630 are preferred, and moreover, compounds described in U.S. Pat. No. 4,552,834
The compounds described in the above are also preferred. These bleach accelerators may be added to light-sensitive materials, and are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for Preservatives for the bleach-fix solution are preferably sulfites, bisulfites, sulfinic acids, or carbonyl bisulfite adducts.

It is preferable for the silver halide color photographic material of the present invention to undergo a water washing and/or stabilization process after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the auxiliary method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5octety of Mo
tion Picture and Televisi
onEngineers 64th SSP, 24B-253
(May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8.542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, Society of Hygiene Technology & Wrv & Sterilization of living things , sterilization,
It is also possible to use fungicides described in "Encyclopedia of Antifungal Agents" by Antifungal Techniques J and Nikki Kanawa, an antifungal agent.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4.
-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a range of 20 seconds to 10 minutes at 15-45°C is selected, preferably 30 seconds to 5 minutes at 25-40'C. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8,543 and 58-
All known methods described in No. 14834 and No. 6 (No. 1220,345) can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the grudge removal process.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Typical compounds that may contain pyrazolidones are JP-A-56-64,339 and JP-A-57-144,547.
No. 58-115.438, etc.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, by lowering the temperature, it is possible to improve the image quality and the stability of the processing solution. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

The method of the present invention can be applied, for example, to the processing of color papers, color direct positive light-sensitive materials, color negative films, and the like. Particularly preferred is application to color paper.

The silver halide emulsion of the light-sensitive material used in the present invention may be of any halogen composition, such as silver iodobromide, silver bromide, silver chlorobromide, or silver chloride.

When performing rapid processing or low replenishment processing, silver chlorobromide emulsions or silver chloride emulsions containing silver chloride of 80 mol % or more are preferred, and silver chloride emulsions containing 90 to 99.9 mol % of silver chloride are preferred. In cases where high sensitivity is required and fog during production, storage, and/or processing must be kept particularly low, salt odor containing 50 mol% or more of silver bromide is particularly preferred. Silver bromide emulsions or silver bromide emulsions are preferred, and more preferably 70 mol % or more. If silver bromide is 90 mol % or more, rapid processing becomes difficult, but means for accelerating development, such as silver halide solutions and fog lazers, are preferred. It is possible to speed up the development to some extent without being limited by the content of silver bromide, and it may be preferable to use a method such as using a development accelerator such as a developer or a developer during processing. In either case, it is not preferable to contain a large amount of silver iodide, and it is sufficient to contain 3 mol % or less of silver iodide.These silver halide emulsions are preferably used mainly in light-sensitive materials for printing such as color paper.

Silver iodobromide and silver chloroiodobromide are preferable for color photosensitive materials for photography (2ga film), and the silver iodide content is 3 to 1.
5 mol% is preferred.

The silver halide grains used in the present invention may have different phases inside and on the surface (core/shell grains), may have a multiphase structure such as a bonded structure, or may have a uniform phase throughout the grain. It is also possible to use a mixture of these.

Average grain size of silver halide grains used in the present invention (
In the case of spherical or near-spherical particles, the particle diameter is used as the particle size, and in the case of cubic particles, the particle size is calculated as the particle size, and is the average based on the projected area.

In the case of tabular grains, the value (expressed in sphere terms) is preferably 2 μm or less and 0.1 μm or more, and particularly preferably 1.5 μm.
It is not more than 0.15 μm.

The particle size distribution can be narrow or wide, but
A so-called monodisperse silver halide emulsion in which the value (variation rate) obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size is within 20%, particularly preferably within 15%, is used in the present invention. In addition, in order to satisfy the target gradation of the light-sensitive material, two or more types of monodisperse silver halide emulsions (monodisperse silver halide emulsions) having different grain sizes are used in emulsion layers having substantially the same color sensitivity. (preferably those having the above-mentioned fluctuation rate) can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, rhombidodecahedral, dodecahedral, etc.).
r) crystals or coexistence of these crystals, or irregular (irregular) crystals such as spherical
It may have a crystalline form (ular), or it may have a composite form of these crystalline forms.

Tabular grains may also be used, especially when the length/thickness ratio is 5.
In particular, tabular grains of 8 or more have a front projected area of 5
An emulsion containing 0% or more may be used, an emulsion consisting of a mixture of these various crystal forms may be used, and these various emulsions may be of a surface latent image type in which a latent image is mainly formed on the surface;
Any type of internal latent image formed inside the particles may be used.

The photographic emulsion used in the present invention is Richichi Disclosure +- (RD) VOl, 176 ItemNα17
643 (L■, ■) (December 1978).

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

Additives used in such processes are listed in Richichi Disclosure Volume 176, Nα 17643 (December 1978) and Volume 187, Ma 18716 (1,97
(November 1999), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

1 Chemical sensitizer 2 Sensitivity enhancer 4 Super sensitizer 5 Brightener 7 Coupler 8 Yes! S Solvent UV absorber Stain inhibitor Dye Image stabilizer Hardener Binder Plasticizer, lubricant R [1 23 pages Same as above 24 pages 25 pages 25 Same as above 25 pages Right column 25 pages 26 pages 26 pages 27 pages RD 648 pages Right column Same as above Same as above Same as above Same as above 650 pages Left to right column Same as above 651 pages Left column Same as above 650 pages Right column Various color couplers can be used in the present invention. Here, the term "color coupler" refers to a compound that can generate a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone, etc. or pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds.6 Specific examples of cyan, magenta, and yellow couplers used in the present invention can be found in Research Disclosure (RD) 17643.
(December 1978) ■-〇 section and 18717
(November 1979).

The color coupler incorporated in the light-sensitive material has a ballast group or is made into a polymer, so that it has diffusion resistance. A two-equivalent color coupler substituted with a leaving group is better than a two-equivalent color coupler in which the coupling active position is a hydrogen atom. Color couplers or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,40
No. 7,210, No. 2.875.057 and No. 3
, 265,506, etc. In the present invention, it is preferable to use a two-equivalent yellow coupler, and U.S. Pat.
No. 3,933.501 and No. 4,022゜62
Yellow couplers with oxygen atom leaving groups described in Japanese Patent Publication No. 55-10739, U.S. Patent No. 4,
No. 401,752, No. 4,326.024, RD1
8053 (April 1979), British Patent No. 1,425
, No. 020, West German Application Publication No. 2,219.91.7,
Typical examples thereof include yellow couplers in which the nitrogen atom h1 is removed, which are described in Japanese Patent No. 2,261,361, Japanese Patent No. 2,329,587, and Japanese Patent No. 2433.812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness.
α-Benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat. Same No. 2゜3
No. 43.703, No. 2.600,788, No. 2,
No. 908,573, No. 3,062,653, No. 3
, No. 152,896 and No. 3936.015. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat. No. 4,351.
The arylthio group described in European Patent No. 897 is preferred, and the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369,879, preferably the pyrazolo[5,1-c)(1,2,43) liazoles described in U.S. Pat. No. 3,725.067, Research Disclosure 24220 ( 1,
Pyrazolotetrazoles and Research Disclosure 24230 (June 1984) and Research Disclosure 24230 (June 1984)
Examples include pyrazolopyrazoles described in June 2013).

Imidazo (1,
2-b) Pyrazoles are preferred, as described in European Patent No. 119,
Pyrazolo[15-b) (1,2,4) described in No. 860
Particular preference is given to triazoles.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, preferably the naphthol-based couplers described in U.S. Pat.
．． No. 212, No. 4゜146.396, No. 4,22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8,233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Patent No. 2,369,929 and U.S. Pat.
No. 01.171, No. 2.772,162, No. 2,
No. 895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat. No. 3,772.
, U.S. Pat.
No. 8,308, No. 4,126,396, No. 4.3
No. 34,011, No. 4,327゜173, West German Patent Publication No. 3,329,729 and Japanese Unexamined Patent Publication No. 1.66/1983
2,5-diacylamino-substituted phenolic couplers described in US Pat. No. 956, etc. and U.S. Pat.
No. 22, No. 4,333,999, No. 4.451,
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 559 and No. 4,427,767.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers include magenta couplers in U.S. Pat. No. 4,366.237 and British Pat. No. 3,234°533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and special couplers described above may form dimers or higher polymers; typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3,451.82.
No. 0 and No. 4,080°211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102.173 and U.S. Patent No. 4.367.2.
It is described in No. 82.

In the various couplers used in the present invention, two types of couplers can be used together in the same layer of the photosensitive layer, or the same compound can be used with different groups in order to satisfy the characteristics required for the photosensitive material. It can also be introduced into two or more layers. When a coupler is used, it is usually dispersed in the oil (high boiling point organic solvent) as described above, but it can also be directly dispersed in a hydrophilic binder without using oil.

Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably 0.001 to 1 mole for yellow couplers. Ol to 0.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

The photographic material used in the present invention is coated on a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper, or a rigid support such as glass. For details on the support and coating method, see Research Disclone+-1F Volume 6 Item 1764
3 Section XV (P.

27) Described in Section M (P, 28) (December 1978 issue).

In the present invention, a reflective support is preferably used.

A "reflective support" is a material that increases the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing dispersed light-reflecting substances such as calcium carbonate and calcium sulfate, and those using a hydrophobic resin containing dispersed light-reflecting substances as a support.

Preferred embodiments are as follows.

(1) The high boiling point organic solvent has the general formula (A), (C), (D)
or (E).

(2) The image forming method according to the claims, in which the color developer does not substantially contain benzyl alcohol.

(Effects of the Invention) Color development can be greatly promoted by the method of the present invention, and D++ax can be sufficiently produced.

Also, development delays can be prevented even in a system in which benzyl alcohol is removed from the color developer.

(Examples) Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in further detail. However, the present invention is not limited to the following examples.

Example 1 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

19.1 g of yellow coupler (E
7) To 0.7g, add 27°2cc of ethyl acetate and the solvent (S
Add 8.2g of o 1v-3) and dissolve this solution to ]0
The mixture was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of sodium dodecylbenzenesulfonate.

- Force field silver bromide emulsion (cubic average grain size 0.88μ,
Particle size distribution variation coefficient 0.08, silver bromide O32 mol%
on the particle surface) and a blue-sensitive sensitizing dye not shown below.
Sulfur sensitization was prepared after addition of 2.0 x 10-' moles per mole of each. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer, and the gelatin hardener for each layer was
Triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer so, e So, 11・N(Ctlls)s S(h ” 50311・N(CJs
) 3 (7.0×10'□S per mole of halogenated
mol) SO, θ 5OsH-N(Cxtl
s) s (each 2.0XIO-' per mole of silver halide
For the red-sensitive emulsion layer, the following compounds were added in 2.6X10-' moles per mole of silver halide. 4.0 x 10-' mole per mole)
and also for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added at 8.5 x 10-' per mole of S halide, respectively. mole, 7.7XIO-' mole, 2.5
X10-' moles were added.

The following dyes were added to the emulsion layer to prevent irradiation.

and third layer (green-sensitive layer) silver chlorobromide emulsion (1:3 mixture (Ag mole) ratio of one with a cubic average grain size of 0.55μ and one with a cubic average grain size of 0°39μ) 0 Coefficient of variation of grain size distribution 0 each .10.0.08, AgBr 0 , 8 mol % was locally contained on the particle surface.

Gelatin magenta coupler (ExM) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-8) Color image stabilizer (Cpd-9) Solvent (Solv-2) Fourth layer (ultraviolet absorption layer) Gelatin ultraviolet absorption Agent (UV-1) Color mixture prevention agent (Cpd-5) Solvent (Solv-5) Fifth layer (red-sensitive layer) (Layer structure) The composition of each layer is shown below, and the numbers indicate the coating amount (g/bo). The silver halide emulsions shown below represent the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Tioz) and a blue dye (ulmarine blue)] -th layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-
1) 0. 1.9 Solvent (Solv-3)
0.35 color image stabilizer (Cpd-7)
0106 Second layer (color mixing prevention N) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (So I
v-1,) O,1,6 solvent (Solv
-4) 0.08 silver chlorobromide emulsion (1:4 mixture (Ag mole) ratio of cubic average grain size 0.58μ and 0.45μ), coefficient of variation of grain size distribution 0.09 each , O, I 1. , 0.6 mol % of AgBr was locally contained in a part of the particle surface.

Gelatin cyan coupler (EχC) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-10) Color image stabilizer (CPd-7) Solvent (Solv-6) Sixth layer (ultraviolet absorption layer) Gelatin ultraviolet absorption Agent (UV-1) Color mixing inhibitor (Cpd-5) Solvent (Solv-5) Seventh N (protective layer) Gelatin 1° (EXC) Cyan coupler Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%) Fluidity Paraffin 0° (ExY) Yellow coupler (Cpd-N Color image stabilizer (ExM) Magenta coupler (Cpd-3) Color image stabilizer (Cpd-7) Color image stabilizer (Cpd-5) Color mixing inhibitor I υ■ (cpa 8) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-9) Color image stabilizer rp (Cp d-10) Color image stabilizer H (Solv-1) Solvent υ1 (LIV-1) !!External radiation absorber 0f ((Solv-2) i8 medium (Solv 3) Solvent 0=P(CJ+v(jgo)') (Solv~4) Solvent Table ■ (Solv 5) Solvent (Solv-6) Dissolution The silver halide photographic material obtained as described above was designated as Sample 1-A.

In the above method r41-A, as shown in Table 1, the exemplified compound of the diffusion-resistant main ingredient represented by the general formula (I) of the present invention was added to the first layer (blue-sensitive layer) in equimolar amounts with yellow coupler, respectively. Similarly, five types of samples (Sample 1-BN2-F) were prepared in which equimolar amounts of magenta coupler were added to the third layer (green-sensitive layer), and cyan coupler was added to the fifth layer (red-sensitive layer). .

After exposing the above photosensitive material through an optical wedge, the following 3
Processed in the next step with a different color developer.

■ Color development 35'C 20 seconds bleach fixing 30-36°C 45 seconds stable ■ 30-37°C 20 seconds stable ■ 30-37°C 20 seconds stable ■ 30-37'C 20 seconds stable ■ 30~ Dry at 37℃ for 30 seconds.Dry at 70-85'C for 60 seconds (stable ■→
■ A four-tank countercurrent system was adopted. ) The composition of each treatment liquid is as follows.

Sakienyu] Tamaryosui 8
00d Ethylenediaminetetraacetic acid 2.0g Benzyl alcohol 15m Triethanolamine 8.0g Sodium chloride 1.4g Potassium carbonate
25gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl 4-aminoaniline 17i acid salt 5.0gN,N-
Diethylhydroxylamine 4,2g 5.6-cyhydroxybenzene-1゜2.4-)risulfonic acid 0.3g Fluorescent brightener (4,4'-diaminostilbene type)
Add 2.0g water
1oootepH (25°C)
10.10 yaw development m Color developer (a) with benzyl alcohol removed.

Left: u1 button (2) N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4=aminoaniline sulfate is removed from color developer (b).

Saradomari Yodo 1 Blood water 4
00dAmmonium thiosulfate (70%) 100
d Sodium sulfite 18g Ammonium ethylenediaminetetraacetic acid (III)
55g ethylenediaminetetraacetic acid disodium
3g glacial acetic acid
Add 8g water and make 1ooo*p
H (25'C) 5.5% constant formalin (37%) 0.1g formalin-sulfite adduct 0.7g 5-chloro-2-
Methyl-4-ifthiazolin-3-one 0.02g2-Methyl-4-isothiazolin-3-one O,01g Sulfuric acid steel
Add 0.005g water
1000#1pH (25°C)
4.0 Table 2 shows the results of measuring the maximum color density and fog density of the blue-sensitive layers of Samples 1-A to 1-F treated with the above three color developing solutions using a Macbeth densitometer. Table 3 shows the measurement results of the maximum color density and fog density of the green sensitive layer.

From Tables 2 and 3, for the blue-sensitive layer and the green-sensitive layer, when processed with color developing agent 0)), the samples of the present invention (Samples 1-B to 1-F) were compared to the comparative example (Sample 1A). In comparison, the fog density is about the same, but there is an acceleration effect that allows the maximum color density to be sufficiently obtained.6 In addition, in the case of color developer (a), that is, a color development processing solution containing benzyl alcohol, a diffusion-resistant main agent is used. The maximum color density of the built-in sampler 4 can be sufficiently obtained. In addition, when processed with color developer (C),
In other words, a developing solution containing neither benzyl alcohol nor a color developing agent hardly develops color.Therefore, the diffusion-resistant color developing agent shown in the present invention does not produce any color, especially when processed with a color developing agent can containing no benzyl alcohol. It gave the best results with little fog (sufficient acceleration effect was observed and a high maximum density could be obtained).

Example 2 In samples 1-A and 1-B of Example 1, the first layer (
Six sample names (Samples 2 to A1 to 2-A
6.2-81 to 2-B6: and samples coated without using a solvent (sample 2-A7.2-87) were prepared in the same manner as in Example 1. Each sample was processed in the same manner as in Example 1 using a color developer (0)), and after the processing, the jil high color density and fog density of the blue-sensitive layer were measured in the same manner as in Example 1. The results are shown in Table 4.

As is clear from Table 4, when the diffusion-resistant color developing agent shown in the present invention is used (Samples 1-B, 2-Bl to
2-B6) An acceleration effect was observed no matter which solvent was used. However, the effect of Chinoku sample 2-83), which was dispersed using the solvent 5-25, was slightly lower.

Claims (1)

[Scope of Claims] 1) A silver halide color photographic material containing a diffusion-resistant coupler and a diffusion-resistant color developing agent on a support; An image forming method characterized by processing with a color developer containing. 2) A silver halide photographic material having a layer in which the diffusion-resistant coupler and the diffusion-resistant color developing agent are emulsified and dispersed in at least one of the high-boiling organic solvents represented by the following general formulas (A) to (E). An image forming method, characterized in that: is processed by the processing method according to claim 1. General formula (A) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (B) W_1-COO-W_2 General formula (C) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (D) ▲ Numerical formulas, chemical formulas, There are tables etc. ▼ General formula (E) W_1-O-W_2 (In the formula, W_1, W_2 and W_3 each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, W_4 is W
_1, OW_1 or S-W_1, n is an integer from 1 to 5, and when n is 2 or more, W_4 may be the same or different from each other, and in the general formula (E),
W_1 and W_2 may form a fused ring)